The conversion of C-H bonds into new functional groups represents a powerful strategy for the synthesis and elaboration of organic molecules. Over the past 20 years, there has been tremendous progress in the development and application of C-H functionalization reactions in organic synthesis. However, despite this progress, selective C-H functionalization can only be achieved in the context of a relatively limited set of organic substrates and C-H sites. One class of substrates that has historically proven challenging for selective C-H functionalization is aliphatic amines. This proposal seeks to address this unmet need through the development of a series of predictable and selective C-H functionalization reactions of aliphatic amines, with a particular focus on saturated nitrogen heterocycles. The proposed efforts will deliver a suite of complementary synthetic methods for the oxidation of C(sp3)-H bonds at sites remote to the amine nitrogen. In each Specific Aim, a different type of metal catalyst will be employed, and a fundamentally different strategy will be used to control site selectivity. As such, the proposed methods will provide a variety of new synthetic disconnections for the construction and derivatization of aliphatic amine-based cores. The overall objective of Aim 1 is to develop Pd-catalyzed ligand-directed reactions for the transannular C-H functionalization of cyclic amines. The overall objective of Aim 2 is to develop metal-oxo/peroxo-catalyzed C(sp3)-H oxidation reactions of amines that proceed with high selectivity for sites remote to nitrogen. Finally, the overall objective of Aim 3 is to employ Pt- catalysis to achieve the sterically selective C-H oxidation of aliphatic amine substrates.